A growing family: New structures of coordination polymers containing adamantane-shaped phosphorus–nitrogen cage ligands

An Improved Synthesis of PN‐adamantanoid Cages P4(NR)6 and a Mechanistic Study of their Fourfold Oxidation

“…Yield=0.958 g (1.180 mmol, 61%). Spectral data matched reported values [9c] . Crystal Data for C 42 H 42 N 6 P 4 ( M =754.69 g/mol): monoclinic, space group C2/c (no.…”

“…The analogous reaction with PhCH 2 N(SiMe 3 ) 2 was also successful and yielded the benzyl substituted cage 1Bn . Compound 1Bn has been made previously, albeit as an impure oil, via salt elimination followed by column chromatographic purification in 32% yield [9c] . Using our route, 1Bn is accessible on essentially any scale in quantitative NMR yield following simple removal of volatile Me 3 SiCl and solvent.…”

“…PCl 3 and all commercial amines were obtained from MilliporeSigma and purified by bulb‐to‐bulb distillation. BnN(TMS) 2 , [26] PhN(TMS) 2 , [27] and 1Et [9c] were prepared following known methods.…”

“…boiling point of Me 3 SiN 3 is 93 °C). Thus, despite their demonstrated potential to serve as valuable tetrahedral tectons, [9b,c,10,13] compounds 1Me and 2Me remain difficult to access, motivating a search for new synthetic developments in this area to unlock their broader study and eventual applied usage.…”

Nitrogen, phosphorus, arsenic, antimony and bismuth

“…49 The reaction of Li(NHBn) with PCl 3 has been shown to afford cages P 4 (NBn) 6 , 19, which may then be employed for the construction of coordination polymers when reacted with CuI. 50 The addition of alkenes 51 and alkynes 52 to ruthenium terminal phosphide complexes has been shown to afford metallaphosphacyclobutanes and metallaphosphacyclobutenes respectively. The insertion of alkynes into niobium-phosphido bonds to give phosphine-substituted alkenyl ligands has been reported.…”